Benzoylbenzoic acids

ABSTRACT

Substituted 3,3-diphenylphthalides, useful as color precursors, particularly in the art of pressure-sensitive duplicating systems, are prepared by condensing substituted 2-benzoylbenzoic acids with substituted anilines.

This invention relates to substituted 3,3-diphenylphthalides useful ascolor precursors, to substituted 2-benzoylbenzoic acids useful asintermediates in preparing said substituted 3,3-diphenylphthalides andto processes for preparing said substituted 3,3-diphenylphthalides.

In its substituted 3,3-diphenylphthalide aspect the invention provides3-(2-X-4-X-phenyl)-3-(2-Y² -4-Y⁴ -phenyl)-4-Z⁴ -5-Z⁵ -6-Z⁶ -7-Z⁷-phthalide of the formula ##STR1## wherein: X is dialkylamino whereinalkyl is non-tertiary alkyl of one to four carbon atoms;

Y² is hydrogen, non-tertiary alkyl of one to four carbon atoms,dialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms, alkanoylamino of two to five carbon atoms or non-tertiary alkoxyof one to four carbon atoms;

Y⁴ is the same as Y² when Y² is dialkylamino, or dialkylamino whereinalkyl is non-tertiary alkyl of one to four carbon atoms, pyrrolidino,piperidino or alkyl(Q--(CH₂)_(n))amino, wherein alkyl is non-tertiaryalkyl of one to four carbon atoms, Q is hydroxy or chloro and n is twoto four when Y² is other than dialkylamino;

Z⁴ is hydrogen or halo;

Z⁵ is the same as Z⁴ ; or non-tertiary alkyl of one to four carbonatoms, nitro, amino, dialkylamino wherein alkyl is non-tertiary alkyl ofone to four carbon atoms or halo when Z⁴, Z⁶ and Z⁷ are each hydrogen;

Z⁶ is the same as Z⁴ ; or non-tertiary alkyl of one to four carbonatoms, nitro, amino, dialkylamino wherein alkyl is non-tertiary alkyl ofone to four carbon atoms or halo when Z⁴, Z⁵ and Z⁷ are each hydrogen;and

Z⁷ is the same as Z⁴.

The compounds of Formula I are useful as color precursors, particularlyin the art of presure-sensitive duplicating systems.

In its substituted 2-benzoylbenzoic acid aspect the invention provides2-(2-Y'² -4-Y'⁴ -benzoyl)-3-Z⁴ -4-Z'⁵ -5-Z'⁶ -6-Z⁷ -benzoic acid of theformula ##STR2## wherein: Y'² is dialkylamino wherein alkyl isnon-tertiary alkyl of one to four carbon atoms, alkanoylamino of two tofive carbon atoms, or non-tertiary alkoxy of one to four carbon atoms;Y'⁴ is the same as Y'² when Y'² is dialkylamino; or dialkylamino whereinalkyl is non-tertiary alkyl of one to four carbon atoms, pyrrolidino,piperidino or alkyl(Q'--(CH₂)_(n))amino, wherein alkyl is non-tertiaryalkyl of one to four carbon atoms, Q' is chloro and n is two to fourwhen Y'² is other than dialkylamino;

Z⁴ is hydrogen or halo;

Z'⁵ is the same as Z⁴ ; or dialkylamino wherein alkyl is non-tertiaryalkyl of one to four carbon atoms when Z⁴, Z'⁶ and Z⁷ are each hydrogen;

Z'⁶ is the same as Z⁴ ; or dialkylamino wherein alkyl is non-tertiaryalkyl of one to four carbon atoms when Z⁴, Z'⁵ and Z⁷ are each hydrogen;

Z⁷ is the same as Z⁴

and acid addition salts thereof.

The compounds of Formula II are useful as intermediates in the followingprocesses for preparing compounds of Formula I.

In one of its process aspects the invention provides the process forpreparing 3-(2-X-4-X-phenyl)-3-(2-Y² -4-Y'⁴ -phenyl)-4-Z⁴ -5-Z"⁵ -6-Z"⁶-7-Z⁷ -phthalide of the formula ##STR3## which comprises condensing2-(2-Y² -4-Y'⁴ -benzoyl)-3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -benzoic acid of theformula ##STR4## with 1-X-3-X-benzene of the formula ##STR5## in contactwith the anhydride of an alkanoic acid of two to five carbon atoms,phosphorus oxychloride or thionyl chloride, wherein:

X is dialkylamino wherein alkyl is non-tertiary alkyl of one to fourcarbon atoms;

Y² is hydrogen, non-tertiary alkyl of one to four carbon atoms,dialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms, alkanoylamino of two to five carbon atoms or non-tertiary alkoxyof one to four carbon atoms;

Y'⁴ is the same as Y² when Y² is dialkylamino; or dialkylamino whereinalkyl is non-tertiary alkyl of one to four carbon atoms, pyrrolidino,piperidino or alkyl(Q'--(CH₂)_(n))amino, wherein alkyl is non-tertiaryalkyl of one to four carbon atoms, Q' is chloro and n is two to fourwhen Y² is other than dialkylamino;

Z⁴ is hydrogen or halo;

Z"⁵ is the same as Z⁴ ; or non-tertiary alkyl of one to four carbonatoms, nitro, dialkylamino wherein alkyl is non-tertiary alkyl of one tofour carbon atoms or halo when Z⁴, Z"⁶ and Z⁷ are each hydrogen;

Z"⁶ is the same as Z⁴ ; or non-tertiary alkyl of one to four carbonatoms, nitro, dialkylamino wherein alkyl is non-tertiary alkyl of one tofour carbon atoms or halo when Z⁴, Z"⁵ and Z⁷ are each hydrogen; and

Z⁷ is the same as Z⁴.

In its other process aspect the invention provides the process forpreparing 3-(2-X-4-X-phenyl)-3-(2-Y² -4-Y'⁴ -phenyl)-4-Z⁴ -5-Z"⁵ -6-Z"⁶-7-Z⁷ -phthalide of Formula III which comprises condensing2-(2-X-4-X-benzoyl)-3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -benzoic acid of theformula ##STR6## with 1-Y² -3-Y'⁴ -benzene of the formula ##STR7## incontact with the anhydride of an alkanoic acid of two to five carbonatoms, phosphorus oxychloride or thionyl chloride, wherein:

X is dialkylamino wherein alkyl is non-tertiary alkyl of one to fourcarbon atoms;

Y² is hydrogen, non-tertiary alkyl of one to four carbon atoms,dialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms, alkanoylamino of two to five carbon atoms or non-tertiary alkoxyof one to four carbon atoms;

Y'⁴ is the same as Y² when Y² is dialkylamino; or dialkylamino whereinalkyl is non-tertiary alkyl of one to four carbon atoms, pyrrolidino,piperidino or alkyl(Q'--(CH₂)_(n))amino, wherein alkyl is non-tertiaryalkyl of one to four carbon atoms, Q' is chloro and n is two to fourwhen Y² is other than dialkylamino;

Z⁴ is hydrogen or halo;

Z"⁵ is the same as Z⁴ ; or non-tertiary alkyl of one to four carbonatoms, nitro, dialkylamino wherein alkyl is non-tertiary alkyl of one tofour carbon atoms or halo when Z⁴, Z"⁶ and Z⁷ are each hydrogen;

Z"⁶ is the same as Z⁴ ; or non-tertiary alkyl of one to four carbonatoms, nitro, dialkylamino wherein alkyl is non-tertiary alkyl of one tofour carbon atoms or halo when Z⁴, Z"⁵ and Z⁷ are each hydrogen; and

Z⁷ is the same as Z⁴.

The foregoing two process aspects of the invention do not providedirectly the compounds of Formula I wherein Y⁴ isalkyl(Q--(CH₂)_(n))amino wherein Q is hydroxy. However, such compoundsare provided by carrying out either of the process aspects of theinvention with the appropriate intermediates wherein Q is hydroxy andthe anhydride of an alkanoic acid of two to five carbon atoms as thecondensing agent, and dealkanoylating the resulting product wherein Q isthe corresponding alkanoyloxy of two to five carbon atoms.

Nor do the foregoing two process aspects of the invention providedirectly the compounds of Formula I wherein Z⁵ or Z⁶ is amino. However,such compounds are provided by carrying out either of the processaspects of the invention with the appropriate intermediates wherein Z⁵or Z⁶ is amino and, if the anhydride of an alkanoic acid of two to fivecarbon atoms is used as the condensing agent, dealkanoylating theresulting product wherein Z⁵ or Z⁶ is the corresponding alkanoylamino oftwo to five carbon atoms.

The generic terms used to define the invention will now be defined.

Non-tertiary alkyl of one to four carbon atoms is methyl, ethyl, propyl,isopropyl, butyl, isobutyl or sec-butyl.

Alkanoylamino of two to five carbon atoms is acetamido propionamido,butyrylamino, isobutyrylamino, valerylamino, isovalerylamino,α-methylbutyrylamino or pivaloylamino.

Non-tertiary alkoxy of one to four carbon atoms is methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.

Halo is fluoro, chloro, bromo or iodo.

The anhydrides of alkanoic acids of two to five carbon atoms are aceticanhydride, propionic anhydride, butyric anhydride, isobutyric anhydride,valeric anhydride, isovaleric anhydride, α-methylbutyric anhydride andpivalic anhydride.

The manner and process of making and using the invention and the bestmode of carrying it out will now be described so as to enable any personskilled in the art to which it pertains to make and use it.

In carrying out the processes of the invention a mixture of 2-(2-Y²-4-Y'⁴ -benzoyl)-3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -benzoic acid of Formula IVand 1-X-3-X-benzene of Formula V or a mixture of2-(2-X-4-X-benzoyl)-3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -benzoic acid of Formula VIand 1-Y² -3-Y'⁴ -benzene of Formula VII and the anhydride of an alkanoicanhydride, preferably acetic anhydride, phosphorus oxychloride orthionyl chloride with or without an inert diluent, is heated at atemperature in the range of 30°-150° C. In some cases the product ofFormula III precipitates from the resulting mixture and may be isolateddirectly. Otherwise the resulting mixture is first acidified with adilute aqueous mineral acid, for example, hydrochloric acid, and thenbasified, for example, with dilute aqueous sodium hydroxide, and theproduct is then isolated.

The compounds of Formula I wherein Z⁵ or Z⁶ is amino are alternativelyprovided by reduction of the corresponding compounds of Formula Iwherein Z⁵ or Z⁶ is nitro with, for example, stannous chloride.

The compounds of Formula I wherein Z⁵ or Z⁶ is nitro are alternativelyprovided by nitration of the corresponding compounds of Formula Iwherein Z⁵ and Z⁶ are hydrogen with, for example, a mixture of nitricacid and sulfuric acid. The nitration can produce the 5-nitro isomer,the 6-nitro isomer or a mixture of both.

The compounds of Formula I wherein Z⁵ or Z⁶ is halo are alternativelyprovided by halogenation of the diazonium salts derived from thecorresponding compounds of Formula I wherein Z⁵ or Z⁶ is amino with, forexample, fluoroboric acid, cuprous chloride, cuprous bromide orpotassium iodide.

As stated above the compounds of Formula I are useful as colorprecursors, particularly in the art of pressure-sensitive duplicatingsystems. Like other color precursors in current use in this art thecompounds of Formula I are colorless under neutral or basic conditions,but become colored when contacted with an acidic material such as silicagel, a phenolic resin or an acidic clay. It is sometimes desired thatthe images produced by such color precursors be copiable by xerographicmeans. A widely used diphenylphthalide color precursor is crystal violetlactone of the formula ##STR8## Crystal violet lactone produces a blueimage which has the advantage of being intense but which suffers thedisadvantage of being poorly copiable by xerographic means. Tocounteract this disadvantage other color precursors have been mixed withcrystal violet lactone as described, for example, in U.S. Pat. No.3,525,630. The images produced by the compounds of Formula I, althoughgenerally less intense in color than the images produced by crystalviolet lactone, are readily copiable by xerographic means. For thisreason the difficulties inherent in using mixed color precursors toachieve xerographic copiability can be avoided by using a compoundFormula I alone.

The compounds of Formula IV and Formula VI, which include among them thecompounds of Formula II, are prepared by condensing the corresponding3-Z⁴ -4-Z"⁵ -5-Z" ⁶ -6-Z⁷ -phthalic anhydrides of the formula ##STR9##with the corresponding 1-Y² -3-Y'⁴ -benzenes of Formula VII or1-X-3-X-benzenes of Formula V, respectively, in contact with a Lewisacid, for example, aluminum chloride or zinc chloride, and with adiluent, for example, benzene, chlorobenzene or o-dichlorobenzene, at atemperature in the range of 20°-200° C. This condensation can produceisomers or mixtures of isomers when the Z"⁵ or Z"⁶ substituent of thecompounds of Formula VIII is alkyl, nitro, dialkylamino or halo. Thusthe derived compounds of Formula IV and Formula VI have the substituentat the 4-position or the 5-position. Compounds of Formula IV or FormulaVI having the substituent in the 4-position or the 5-position producethe corresponding compounds of Formula I having the substituent in the 5-position or the 6-position.

Acid addition salts of the compounds of Formula II, Formula IV andFormula VI can be prepared with inorganic (mineral) or organic acids. Ifinorganic, the acid can be, for example, hydrochloric acid, hydrobromicacid, nitric acid, phosphoric acid, sulfuric acid or sulfamic acid. Iforganic, the acid can be, for example, acetic acid, glycolic acid,lactic acid, quinic acid, hydrocinnamic acid, succinic acid, tartaricacid, citric acid, methanesulfonic acid or benzenesulfonic acid.

The molecular structures of the compounds of Formula I, Formula II,Formula IV and Formula VI follow from the structures of the compounds ofFormula V, Formula VII and Formula VIII and the synthetic method and maybe identified and corroborated by observation of one or more of thefollowing physical properties: color, melting point (m.p.), solubilitybehavior, acid-base behavior, thin layer chromatographic spectrum,infrared spectrum, mass spectrum, nuclear magnetic resonance spectrumand ultraviolet spectrum.

The compounds of Formula VIII wherein Z⁴ is halo and Z"⁵ or Z"⁶ is nitroor halo are known. Some of the compounds of Formula VIII wherein Z"⁵ orZ"⁶ is dialkylamino are also known. Those which are not known can beprepared, for example, according to the method of U.S. Pat. No.2,597,965 starting with diethyl 4-aminophthalate and, successively,appropriately N-alkylating, de-ethylating and cyclizing.

Some of the compounds of Formula V and the compounds of Formula VIIwherein Y² is dialkylamino are known. Those which are not known can beprepared, for example, by appropriately N-alkylating m-phenylenediamine.

Some of the compounds of Formula VII wherein Y² is hydrogen are known.Those which are not known can be prepared by appropriately N-alkylatinganiline.

Some of the compounds of Formula VII wherein Y² is alkyl are known.Those which are not known can be prepared, for example, starting withthe appropriate alkylbenzene and, successively, 4-nitrating, reducingthe nitro to amino, N-acetylating, 3-nitrating, deacetylating,deaminating, reducing the nitro to amino and appropriately N-alkylating.

Some of the compounds of Formula VII wherein Y² is alkanoylamino areknown. Those which are not known can be prepared, for example, startingwith m-nitroaniline and, successively, N-alkanoylating, reducing thenitro to amino and appropriately N-alkylating.

Some of the compounds of Formula VII wherein Y² is alkoxy are known.Those which are not known can be prepared, for example, starting withm-hydroxyacetanilide and, successively, appropriately O-alkylating,deacetylating and appropriately N-alkylating.

The foregoing methods also provide the corresponding compounds ofFormula VII wherein Y'⁴ is alkyl(hydroxy-(CH₂)_(n))amino which are notknown.

The following examples illustrate the invention.

EXAMPLE 1

A. A mixture of phthalic anhydride (30 g.), N,N-dimethylaniline (60.5g.), aluminum chloride (60 g.) and chlorobenzene (180 g.) was heated (to75° C.) during one hour, then cooled. Ice (500 ml.) was added, thechlorobenzene layer was separated and the chlorobenzene was steamdistilled. Addition of base to a solution of the residue in dilutesulfuric acid afforded 2-(4-(dimethylamino)benzoyl)benzoic acid (IV: Y²═ Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ H, Y'⁴ ═ (CH₃)₂ N).

B. A mixture of 2-(4-(dimethylamino)benzoyl)benzoic acid (26.8 g.),N,N,N',N'-tetramethyl-m-phenylenediamine (16.4 g.) and acetic anhydride(80 g.) was heated (to 95° C.) during one hour, cooled and poured intodilute hydrochloric acid. The resulting mixture was basified.Recrystallization of the resulting solid from a mixture of toluene andhexane afforded3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) (m.p. 190°-194° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)phthalideformed a gray-black image which was xerographically copiable.

C. Substituting N,N,N',N'-tetra(sec-butyl)-m-phenylenediamine (preparedby N-alkylating m-phenylenediamine with sec-butyl bromide) forN,N,N',N'-tetramethyl-m-phenylenediamine in part B of this example,there is obtained3-(2,4-bis(di-sec-butylamino)phenyl)-3-(4-(dimethylamino)phenyl)phthalide(I: X ═ (CH₃ CH₂ (CH₃)CH)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H, Y⁴ ═ (CH₃)₂N).

EXAMPLE 2

A. In a manner similar to that of part A of Example 1 condensation ofphthalic anhydride (60 g.) and N,N-diethyl-m-toluidine (162.8 g.) incontact with aluminum chloride (120 g.) and with chlorobenzene (360 ml.)as diluent afforded 2-(2-methyl-4-(diethylamino)benzoyl)benzoic acid(IV: Y² ═ CH₃, Y'⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ H).

B. In a manner similar to that of part B of Example 1 condensation of2-(2-methyl-4-(diethylamino)benzoyl)benzoic acid (25 g.) andN,N,N',N'-tetramethyl-m-phenylenediamine (13.2 g.) in contact withacetic anhydride (75 g.) and recrystallization of the resulting productafforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) ina first crop from toluene (m.p. 204°-206° C.) and in a second crop froma mixture of toluene and hexane (m.p. 191°-195° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)phthalideformed a violet-gray image which was xerographically copiable.

C. Substituting m-butyl-N,N-dimethylaniline (prepared by N-methylatingm-butylaniline with dimethyl sulfate) for N,N-diethyl-m-toluidine inpart A of this example, there is obtained2-(2-butyl-4-(dimethylamino)benzoyl)benzoic acid (IV: Y² ═ CH₃ CH₂ CH₂CH₂, Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ H).

D. Substituting 2-(2-butyl-4-(dimethylamino)benzoyl)benzoic acid for2-(2-methyl-4-(diethylamino)benzoyl)benzoic acid in part B of thisexample, there is obtained3-(2,4-bis(dimethylamino)phenyl)-3,(2-butyl-4-(dimethylamino)phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ CH₃ CH₂ CH₂ CH₂, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H).

EXAMPLE 3

A. A mixture of phthalic anhydride (5.92 g.),N,N,N',N'-tetramethyl-m-phenylenediamine (6.56 g.), zinc chloride (5.40g.) and chlorobenzene (70 ml.) was heated under reflux for 3 hours. Thechlorobenzene was decanted and the residue was air-dried. A solution ofthe residue in dilute hydrochloric acid (10%, 20 ml. plus 20 ml. ofwater) was diluted with more water (20 ml.), affording2-(2,4-bis(dimethylamino)benzoyl)benzoic acid (II: Y'² ═ Y'⁴ ═ (CH₃)₂ N,Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H) dihydrochloride trihydrate (4 g., m.p.136°-141° C.; after recrystallization from ethanol, m.p. 140°-141° C.).In another preparation the free base (m.p. 165°-168° C.) was obtainedunder less acidic conditions (pH 4 -6).

B. A mixture of crude 2-(2,4-bis(dimethylamino)benzoyl)benzoic acid (7g.), N,N,N',N'-tetramethyl-m-phenylenediamine (1.64 g.) and aceticanhydride was warmed (at 25°-35° C.) during 2 to 3 hours, then pouredinto dilute hydrochloric acid (10%). The resulting mixture was basifiedand filtered with a filter aid. The filter cake was extracted with hottoluene. Dilution of the toluene extract with hexane afforded3,3-bis(2,4-bis(dimethylamino)phenyl)phthalide (I: X ═ Y² ═ Y⁴ ═ (CH₃)₂N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) m.p. 186°-188° C.).

When applied to silica gel or standard field resin3,3-bis(2,4-bis(dimethylamino)phenyl)phthalide formed a red-brown imagewhich was xerographically copiable.

C. Substituting N,N,N',N'-tetra(sec-butyl)-m-phenylenediamine forN,N,N',N'-tetramethyl-m-phenylenediamine in part A of this example,there is obtained 2-(2,4-bis(di-sec-butylamino)benzoyl)benzoic acid (II:Y'² ═ Y'⁴ ═ (CH₃ CH₂ (CH₃)CH)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H).

D. Substituting N,N-diethyl-m-toluidine forN,N,N',N'-tetramethyl-m-phenylenediamine in part B of this example,there is obtained3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)phthalide,the compound of part B of Example 2.

E. Substituting N-phenylpyrrolidine, N-phenylpiperidine orN-ethyl-N-(3-chloropropyl)aniline forN,N,N',N'-tetramethyl-m-phenylenediamine in part B of this example,there are obtained, respectively,3-(2,4-bis(dimethylamino)phenyl)-3-(4-pyrrolidinophenyl)phthalide##STR10##3-(2,4-bis(dimethylamino)phenyl)-3-(4-piperidinophenyl)phthalide##STR11## and3-(2,4-bis(dimethylamino)phenyl)-3(4-(ethyl(3-chloropropyl)amino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H, Y⁴ ═ CH₃ CH₂ (Cl(CH₂)₂)N).

EXAMPLE 4

A. In a manner similar to that of part B of Example 3 condensation of2-(2,4-bis(dimethylamino)benzoyl)benzoic acid (2.4 g.) andm-(dimethylamino)acetanilide (1.42 g.) and recrystallization of part ofthe product from a mixture of toluene, ligroin and hexane and part froma mixture of ethyl acetate and hexane afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-acetamido-4-(dimethylamino)phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ CH₃ CONH, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) (m.p.97°-136° C.).

When applied to standard field resin3-(2,4-bis(dimethylamino)phenyl)-3-(2-acetamido-4-(dimethylamino)phenyl)phthalideformed a red-blue-brown image which was xerographically copiable.

B. Substituting m-(dimethylamino)-2,2-dimethylpropionanilide (preparedby N-alkanoylating N,N-dimethylphenylenediamine with pivaloyl chloride)for m-(dimethylamino)acetanilide in part A of this example, there isobtained3-(2,4-bis(dimethylamino)phenyl)-3-(2-pivaloylamino-4-(dimethylamino)phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ (CH₃)₃ CCONH, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H).

C. Condensation of phthalic anhydride and m-(dimethylamino)acetanilideby the method of part A of Example 1 affords2-(2-acetamido-4-(dimethylamino)benzoyl)benzoic acid (II: Y'² ═ CH₃CONH, Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H).

D. Condensation of 2-(2-acetamido-4-(dimethylamino)benzoyl)benzoic acidand N,N,N',N'-tetramethyl-m-phenylenediamine by the method of part B ofExample 1 affords3-(2,4-bis(dimethylamino)phenyl)-3-(2-acetamido-4-(dimethylamino)phenyl)phthalide,the compound of part A of this example.

EXAMPLE 5

A. In a manner similar to that of part A of Example 1 condensation ofphthalic anhydride (15 g.) and m-ethoxy-N,N-diethylaniline (19 g.) incontact with aluminum chloride (15 g.) and with o-dichlorobenzene asdiluent afforded 2-(2-ethoxy-4-(diethylamino)benzoyl)benzoic acid (II:Y'² ═ CH₃ CH₂ O, Y'⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z'⁴ ═ Z'⁶ ═ Z⁷ ═ H) (11 g.,m.p. 174°-181° C.).

B. A mixture of 2-(2-ethoxy-4-(diethylamino)benzoyl)benzoic acid (6.82g.), N,N,N',N'-tetramethyl-m-phenylenediamine (2.80 g.) and aceticanhydride (20 g.) was heated (70°-75° C.) during one hour, let standovernight and poured into dilute hydrochloric acid. The resultingmixture was basified. Recrystallization of the resulting red precipitatefrom hexane followed by slurrying in alkaline water afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-ethoxy-4-(diethylamino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃ CH₂ O, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z⁵ ═ Z.sup. 6═ Z⁷ ═ H) (m.p. 146°-150° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(2-ethoxy-4-(diethylamino)phenyl)phthalideformed a blue-black image which was xerographically copiable.

C. Substituting m-isobutoxy-N,N-dimethylaniline (prepared byO-alkylating m-hydroxyacetanilide with isobutyl bromide, thendeacetylating the resulting m-isobutoxyacetanilide, then N-alkylatingthe resulting m-isobutoxyaniline with methyl sulfate) form-ethoxy-N,N-diethylaniline in part A of this example, there is obtained2-(2-isobutoxy-4-(dimethylamino)benzoyl)benzoic acid (II: Y'² ═ (CH₃)₂CHCH₂ O, Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H).

D. Substituting 2-(2-isobutoxy-4-(dimethylamino)benzoyl)benzoic acid for2-(2-ethoxy-4-(diethylamino)benzoyl)benzoic acid in part B of thisexample, there is obtained3-(2,4-bis(dimethylamino)phenyl)-3-(2-isobutoxy-4-(dimethylamino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ (CH₃)₂ CHCH₂ O, Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷═ H).

E. Condensation of phthalic anhydride and N-(m-anisyl)pyrrolidine(prepared from m-anisidine and 1,4-dibromobutane),N-(m-anisyl)piperidine (prepared from m-anisidine and1,5-dibromopentane) or N-methyl-N-(2-chloroethyl)-m-anisidine (preparedfrom N-methyl-m-anisine and 1-bromo-2-chloroethane) by the method ofpart A of Example 1 affords, respectively,2-(2-methoxy-4-pyrrolidinobenzoyl)benzoic acid ##STR12##2-(2-methoxy-4-piperidinobenzoyl)benzoic acid ##STR13## and2-(2-methoxy-4-(methyl(2-chloroethyl)amino)benzoyl)benzoic acid (II: Y'²═ CH₃ O, Y'⁴ ═ CH₃ (ClCH₂ CH₂)N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z'⁷ ═ H).

F. Condensation of 2-(2-methoxy-4-pyrrolidinobenzoyl)benzoic acid,2-(2-methoxy-4-piperidinobenzoyl)benzoic acid or2-(2-methoxy-4-(methyl(2-chloroethyl)amino)benzoyl)benzoic acid withN,N,N',N'-tetramethyl-m-phenylenediamine by the method of part B ofExample 1 affords, respectively,3-(2,4-bis(dimethylamino)phenyl)-3-(2-methoxy-4-pyrrolidinophenyl)phthalide##STR14##3-(2,4-bis(dimethylamino)phenyl)-3-(2-methoxy-4-piperidinophenyl)phthalide##STR15## and3-(2,4-bis(dimethylamino)phenyl)-3-(2-methoxy-4-(methyl(2-chloroethyl)amino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃ O, Y⁴ ═ CH₃ (ClCH₂ CH₂)N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═H).

EXAMPLE 6

A. In a manner similar to that of part A of Example 1 condensation oftetrachlorophthalic anhydride (21.4 g.) and N,N-diethyl-m-toluidine (41g.) in contact with aluminum chloride (30 g.) and with o-dichlorobenzene(90 ml.) as diluent afforded2-(2-methyl-4-(diethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid(IV: Y² ═ CH₃, Y'⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ Cl) (26 g.,m.p. 117° C. with sublimation).

B. In a manner similar to that of part B of Example 1 condensation of2-(2-methyl-4-(diethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid(22.4 g.) and N,N,N',N'-tetramethyl-m-phenylenediamine (8.20 g.) incontact with acetic anhydride (75 g.) and recrystallization of theresulting product from toluene afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-4,5,6,7-tetrachlorophthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Cl)(m.p. 236°-238° C.; after slurrying in acetone, 237°-239° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-4,5,6,7-tetrachlorophthalideformed an image which was xerographically copiable.

EXAMPLE 7

A. In a manner similar to that of part A of Example 3 condensation oftetrachlorophthalic anhydride (1.92 g.) andN,N,N',N'-tetramethyl-m-phenylenediamine (1.64 g.) in contact with zincchloride (1.35 g.) and with chlorobenzene (40-45 ml.) as diluentafforded 2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoicacid (II: Y'² ═ Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ Cl) (m.p.199°-201° C.).

B. A mixture of most of the2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid frompart A of this example, N,N,N',N'-tetramethyl-m-phenylenediamine (0.82g. plus 0.4 g.) and acetic anhydride was heated under reflux.Concentration of a toluene extract of the resulting product gave a tar,which was slurried in hexane, affording3,3-bis(2,4-bis(dimethylamino)phenyl-4,5,6,7-tetrachlorophthalide (I: X═ Y² ═ Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Cl) (m.p. 195°-197° C.).

When applied to acidic clay3,3-bis(2,4-bis(dimethylamino)phenyl)-4,5,6,7-tetrachlorophthalideformed a red-blue image which was xerographically copiable.

C. Substituting tetrafluorophthalic anhydride, tetrabromophthalicanhydride or tetraiodophthalic anhydride for tetrachlorophthalicanhydride in part A of this example, there are obtained, respectively,2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrafluorobenzoic acid (II:Y'² ═ Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ F),2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrabromobenzoic acid (II:Y'² ═ Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ Br) and2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetraiodobenzoic acid (II: Y'²═ Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z'⁷ ═ I).

D. Substituting2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrafluorobenzoic acid,2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrabromobenzoic acid or2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetraiodobenzoic acid for2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid inpart B of this example, there are obtained, respectively,3,3-bis(2,4-bis(dimethylamino)phenyl)-4,5,6,7-tetrafluorophthalide (I: X═ Y² ═ Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ F), 3,3-bis(2,4-bis(dimethylamino)phenyl)-4,5,6,7-tetrabromophthalide (I: X ═ Y² ═ Y⁴ ═(CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Br) and3,3-bis(2,4-bis(dimethylamino)phenyl)-4,5,6,7-tetraiodophthalide (I: X ═Y² ═ Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ I).

EXAMPLE 8

Three portions of a mixture of concentrated nitric acid (0.6 ml. eachportion) and concentrated sulfuric acid (0.66 ml. each portion) wereadded to a mixture of3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)phthalide(4.17 g.) and concentrated sulfuric acid (20 ml.) with cooling. Aftereach addition the temperature was allowed to rise to room temperature.The resulting mixture was poured onto ice and the resulting mixture wasbasified, affording3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-5 or6-nitrophthalide (I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁷ ═ H, Z⁵ or Z⁶ ═ O₂N and the other of Z⁵ or Z⁶ ═ H) or a mixture of both.

When applied to silica gel3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-5 or6-nitrophthalide formed a gray-black image which was xerographicallycopiable.

EXAMPLE 9

In a manner similar to that of Example 8 nitration of3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)phthalide(4.57 g.) afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-5or 6-nitrophthalide (I: X ═ (CH₃)₂ N, Y² ═ CH₃, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═Z⁷ ═ H, Z⁵ or Z⁶ ═ O₂ N and the other of Z⁵ or Z⁶ ═ H) or a mixture ofboth.

When applied to silica gel3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-5or 6-nitrophthalide formed a gray-black image which was xerographicallycopiable.

EXAMPLE 10

A. Stannous chloride dihydrate (6.7 g.) was added slowly to a mixture ofmost of the product of Example 8 and concentrated hydrochloric acid (50ml.) with heating (60° C.). After one hour the resulting mixture wascooled, made alkaline and filtered, affording3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-5 or6-aminophthalide (I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁷ ═ H, Z⁵ or Z⁶ ═ H₂N and the other of Z⁵ or Z⁶ ═ H) or a mixture of both.

When applied to silica gel3-(2,4-bis(dimethylamino)phenyl-3-(4-(dimethylamino)phenyl)-5 or6-aminophthalide formed a gray-violet or gray-brown image which wasxerographically copiable.

B. Condensation of 4-aminophthalic anhydride andN,N,N',N'-tetramethyl-m-phenylenediamine by the method of part A ofExample 3 affords 2-(2,4-bis(dimethylamino)benzoyl)-5-aminobenzoic acid.

C. Condensation of 2-(2,4-bis(dimethylamino)benzoyl)-5-aminobenzoic acidand N,N,N',N'-tetramethyl-m-phenylenediamine by the method of part B ofExample 3 and deacetylation of the resulting product affords3,3-(2,4-bis(dimethylamino)phenyl)-6-aminophthalide (I: X ═ Y² ═ Y⁴ ═(CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ H₂ N).

EXAMPLE 11

In a manner similar to that of Example 10 reduction of most of theproduct of Example 9 afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-5or 6-aminophthalide (I: X ═ (CH₃)₂ N, Y² ═ CH₃, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═Z⁷ ═ H, Z⁵ or Z⁶ ═ H₂ N and the other of Z⁵ or Z⁶ ═ H) or a mixture ofboth.

When applied to silica gel3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-5or 6-aminophthalide formed a gray-violet or gray-black image which wasxerographically copiable.

EXAMPLE 12

A. A mixture of 4-(dimethylamino)phthalic anhydride (7 g.),N,N-dimethylaniline (9.12 g.), aluminum chloride (11.7 g.) and benzene(36.5 ml.) was stirred (for 10 min.) at ice-bath temperature, thenovernight at room temperature. The mixture was then extracted withdilute sulfuric acid (20%, 80 ml.). Adjustment of the pH of the acidicextract to 5 afforded a mixture of2-(4-(dimethylamino)benzoyl)-4-(dimethylamino)benzoic acid (IV: Y² ═ Z⁴═ Z"⁶ ═ Z⁷ ═ H, Y'⁴ ═ Z"⁵ ═ (CH₃)₂ N) and2-(4-(dimethylamino)benzoyl)-5-(dimethylamino)benzoic acid (IV: Y² ═ Z⁴═ Z"⁵ ═ Z⁷ ═ H, Y'⁴ ═ Z"⁶ ═ (CH₃)₂ N) (6.3 g.).

B. A mixture of part (3.12 g.) of the mixture of products from part A ofthis example, N,N,N',N'-tetramethyl-m-phenylenediamine (1.5 g.) andacetic anhydride (20 g.) was heated (to 85° C.), then cooled. Theresulting precipitate was washed with ether, washed with alkali andrecrystallized from acetone, affording3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-5-(dimethylamino)phthalide(I: X ═ Y⁴ ═ Z⁵ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁶ ═ Z⁷ ═ H) (m.p. 222°-225° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(4-dimethylamino)phenyl)-5-(dimethylamino)phthalideslowly formed a blue-gray image which was xerographically copiable.

C. The acetic anhydride filtrate from part B of this example was treatedfirst with dilute hydrochloric acid (16 g. of concentrated acid plus 80g. of water), then basified, affording3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-6-(dimethylamino)phthalide(I: X ═ Y⁴ ═ Z⁶ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁷ ═ H) (m.p. 182°-185° C.after purification).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-6-(dimethylamino)phthaliderapidly formed a violet-purple image which was xerographically copiable.

D. Propionic anhydride, phosphorus oxychloride or thionyl chloride canbe substituted for acetic anhydride in part B of this example.

EXAMPLE 13

A. In a manner similar to that of part A of Example 3 condensation of4-(dimethylamino)phthalic anhydride (1.91 g.) andN,N,N',N'-tetramethyl-m-phenylenediamine (1.64 g.) in contact with zincchloride (2.70 g.) and with chlorobenzene (50 ml.) as diluent afforded2-(2,4-bis(dimethylamino)benzoyl)-4-(dimethylamino)benzoic acid (II: Y'²═ Y'⁴ ═ Z'⁵ ═ (CH₃)₂ N, Z⁴ ═ Z'⁶ ═ Z⁷ ═ H) (m.p. 216°-222° C.) or the5-(dimethylamino) isomer thereof.

B. In a manner similar to that of part B of Example 3 condensation of2-(2,4-bis(dimethylamino)benzoyl)-4-(dimethylamino)benzoic acid or the5-(dimethylamino) isomer thereof (10 g.) andN,N,N',N'-tetramethyl-m-phenylenediamine (2.30 g.) and crystallizationof the product from toluene afforded3,3-bis(2,4-bis(dimethylamino)phenyl)-5-(dimethylamino)phthalide (I: X ═Y² ═ Y⁴ ═ Z⁵ ═ (CH₃)₂ N, Z⁴ ═ Z⁶ ═ Z⁷ ═ H) (m.p. 188°-192° C.) or the6-(dimethylamino) isomer thereof.

C. Substituting N-ethyl-N-(4-hydroxybutyl)aniline forN,N,N',N'-tetramethyl-m-phenylenediamine in part B of this example anddeacetylating the resulting product, there is obtained3-(2,4-bis(dimethylamino)phenyl)-3-(4-(ethyl(4-hydroxybutyl)amino)phenyl)-5-(dimethylamino)phthalide(I: X ═ Z⁵ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁶ ═ Z⁷ ═ H, Y⁴ ═ CH₃ CH₂ (HO(CH₂)₄)N)or the 6-(dimethylamino) isomer thereof.

D. Substituting 4-methylphthalic anhydride, 4-nitrophthalic anhydride or4-chlorophthalic anhydride for 4-(dimethylamino)phthalic anhydride inpart A of this example, there are obtained, respectively,2-(2,4-bis(dimethylamino)benzoyl)-5-methylbenzoic acid (VI: X ═ (CH₃)₂N, Z⁴ ═ Z"⁵ ═ Z⁷ ═ H, Z"⁶ ═ CH₃),2-(2,4-bis(dimethylamino)benzoyl)-5-nitrobenzoic acid (VI: X ═ (CH₃)₂ N,Z⁴ ═ Z'⁵ ═ Z⁷ ═ H, Z'⁶ ═ O₂ N) and2-(2,4-bis(dimethylamino)benzoyl-5-chlorobenzoic acid (VI: X ═ (CH₃)₂ N,Z⁴ ═ Z'⁵ ═ Z⁷ ═ H, Z'⁶ ═ Cl).

E. Substituting 2-(2,4-bis(dimethylamino)benzoyl)-5-methylbenzoic acid,2-(2,4-bis(dimethylamino)benzoyl)-5-nitrobenzoic acid or2-(2,4-bis(dimethylamino)benzoyl)-5-chlorobenzoic acid for2-(2,4-bis(dimethylamino)benzoyl)-5-(dimethylamino)benzoic acid in partB of this example, there are obtained, respectively,3,3-bis(2,4-bis(dimethylamino)phenyl)-6-methylphthalide (I: X ═ Y² ═ Y⁴═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ CH₃),3,3-bis(2,4-bis(dimethylamino)phenyl)-6-nitrophthalide (I: X ═ Y² ═ Y⁴ ═(CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ O₂ N) and3,3-bis(2,4-bis(dimethylamino)phenyl)-6-chlorophthalide (I: X ═ Y² ═ Y⁴═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ Cl).

EXAMPLE 14

Sodium nitrite is added to a mixture of3,3-bis(2,4-bis(dimethylamino)phenyl)-6-aminophthalide in dilutehydrobromic acid. The resulting mixture is added to a solution ofcuprous bromide in dilute hydrobromic acid, affording, afterbasification, 3,3-bis(2,4-bis(dimethylaminophenyl)-6-bromophthalide (I:X ═ Y² ═ Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ Br).

What is claimed is: 1.2-(2,4-Bis(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid. 2.2-(2,4-Bis(dimethylamino)benzoyl-4-(dimethylamino)benzoic acid. 3.2-(2,4-Bis(dimethylamino)benzoyl)-5-(dimethylamino)benzoic acid.